Патент USA US3025153код для вставки
iJite tates U! ate 3,025,147 Patented Mar. 13, 1962 1 2 3,025,147 cent ASTM distillation point not greater than about 220° F, as such gasolines normally involve a severe engine NONSTALLING GASGLINE CQMPUSHTIQN Gardner E. Gaston, Tarentum, and Donald W. Howard, stalling problem. The amine salts and polyoxyalkylene derivatives of stabilized rosin amines whose use is included by this in vention are polar, surface active materials‘. While the invention is not limited to any theory of operation, it Monroeville, Pa., assignors to Gulf Research & Devel opment Company, Pittsburgh, Pa., a corporation of Delaware No Drawing. Filed Aug. 1, 1953, Ser. No. 752,442 ' it Q 8 Claims. might appear that the addition agents disclosed herein, by (Cl. 44-62) virtue of their polarity, tend to orient themselves upon the metal surfaces of the throttle valve and other critical car This invention relates to gasoline fuel compositions, and more particularly to gasoline fuel compositions that have 10 buretor parts contacted by the gasoline compositions, thus reduced engine stalling tendencies at cool, humid atmos forming a moisture-displacing residual coating upon said pheric conditions. carburetor parts which tend to prevent the adherence to When an internal combustion engine is operated at cool, said metal surfaces of accumulations of ice of such magni humid atmospheric conditions, using a gasoline fuel hav tude as to block the narrow air passages that exist in ing a relatively low 50 percent ASTM distillation point, carburetor throats at engine idling conditions. It is also i.e., below about 235° F., excessive engine stalling is apt considered possible that the addition agents disclosed here to be encountered at idling speeds during the warm-up in may tend to orient themselves about small, ice particles, period, especially where engine idling occurs following a thus tending to prevent the formation of macrocrystals of period of light load operation. Engine stalling under ice of a size sufficient to block carburetor air passages at such conditions has been attributed to the partial or com 20 engine idiing conditions. Although the effectiveness of tete blocking of the narrow air passage that exists be the herein disclosed addition agents is believed to be at tween the carburetor throat and the carburetor throttle tributable in some way to the particular polar, surface valve during engine idling, by ice particles and/or solid active characteristics thereof, this general explanation is hydrocarbon hydrates that deposit upon and adhere to somewhat negatived by the fact that many other surface the metal surfaces of the carburetor parts. Such icing of 25 active agents, including, for example, other salts and oxy carburetor parts occurs as a result of the condensation of moisture from the air drawn into the carburetor and as a result of the solidi?cation of such condensed moisture. The aforesaid condensation and solidi?cation of moisture are caused by the refrigerating effect of rapidly evapo rating gasoline. Accordingly, excessive engine stalling due to carburetor icing occurs as a practical matter only in the aikylene derivatives of stabilized rosin amines, as well as salts of other amines than rosin amines, have little or no effect upon the carburetor icing tendencies of gasolines. 30 The antistalling addition agents disclosed herein are useful when incorporated in gasoline compositions of the type disclosed in any amount su?icient to reduce the engine stalling characteristics thereof. For example, an instance of gasolines containing a large proportion of improvement in the stalling characteristics of gasolines relatively highly volatile components. in practice, the of'the type dis-closed herein will normally be obtained by problem of engine stalling due to carburetor icing has 35 addition thereto of the herein disclosed addition agents been found to be serious, under cool, humid atmospheric in amounts of at least 0.001 percent by weight of the conditions, in connection with gasolines having a 50 per composition (approximately 2.5 to 2.6 lbs/1000 bbls. of cent ASTM distillation point below about 220° F. gasoline). Preferably the antistalling addition agents Excessive engine stalling is, of course, a source of an disclosed herein will be employed in proportions of at 40 noyance owing to the resulting increased fuel consump least 0.006 percent by weight of the composition (ap tion, battery wear and inconvenience of frequent restart— proximately 15 lbs./1000 bbls. of gasoline). Thus, a ing. It is therefore important that the inherent engine stalling characteristics of gasoline fuel be reduced sub stantially, where the 50 percent ASTM distillation point marked improvement in the stalling characteristics of gasolines has been obtained by incorporation therein of tions that comprise hydrocarbon mixtures boiling in the pounds per thousand barrels of gasoline. addition agents of the kind disclosed herein in propor of such gasoline fuels is sufficiently low to cause a prob 45 tions of about 15 to 25 pounds per thousand barrels of lem in this respect. gasoline. Normally, we prefer to employ the addition The present invention relates to gasoline fuel composi agents disclosed herein in proportions of about 15 to 50 Although in gasoline range and that normally tend to promote engine some instances, it may be desired to employ the antistall stalling by carburetor icing, which fuel compositions ex 50 ing addition agents disclosed herein in amounts in excess hibit reduced engine stalling tendencies, and which are of 250 pounds per thousand barrels of gasoline, that is thereby rendered more suitable for use as fuels in spark 0.1 percent by weight or higher, such proportions are not ignition, reciprocating internal combustion engines. We necessary and normally produce'no signi?cant additional have found that such improved gasoline compositions can improvement in the stalling characteristics of the gasoline. be obtained by incorporating therein a small amount of 55 111 no instance sohuld the antistalling addition agents dis an addition salt of a stabilized rosin amine and an oil soluble hydrocarbon sulfonic acid, or by incorporating therein a small amount of a polyoxyalkylene derivative of a stabilized rosin amine containing per molecule about 4 closed herein be added to gasoline in amounts such as to produce an undue adverse effect on the volatility, com bustibility, antiknock or gum-forming characteristics of the gasoline. to 20, preferably 5 to 15, oxyalkylene groups that con 60 It will be appreciated that the optimum proportion of tain 2 to 3 carbon atoms each. Salts of dehydroabietyl the antistalling addition agents disclosed herein can vary amine and oil-soluble petroleum sulfonic acids are ex within the range indicated above in accordance with the amples of preferred salts whose use is included by this particular gasoline employed, inasmuch as the problem invention. The polyoxyethylene derivative of dehydro of engine stalling due to carburetor icing is a function of abietylamine that contains about 11 oxyethylene groups 65 the 50 percent ASTM distillation point of the gasoline. per molecule is an example of another especially effective Thus, greater concentrations of the antistalling addition material for the purposes of this invention. The above agents are normally desirable with decreasing 50 percent indicated addition agents are normally employed in pro ASTM distillation points. The optimum concentration of portions between about 0.001 and 0.01 percent by weight, the lantistalling addition agents disclosed herein may also but other proportions canbe used. The invention is im 70 vary somewhat in accordance with the particular make portant in connection with gasolines having a 50 per and model of engine in which the gasoline is used, as 3,025,147 3 - 4 Inspections: well as in accordance with the severity of the atmos pheric conditions encountered. With regard to this last Vapor pressure, Reid, lb ________________ __ 8.5 ASTM, distillation, gasoline mentioned factor, the problem of engine stalling due to carburetor icing resulting from the refrigerating e?ect of evaporating gasoline upon moisture condensed from the atmosphere has been found to ‘be serious at low tempera Over pt. ° F _______________________ __ End pt. ° F ________________________ __ 100 357 10% evaporated at ° F ______________ __ 136 50% evaporated at ° F ______________ __ 200 tures, e.g., 35°, 40°, 45°, 50°, and when the relative hu 90% evaporated at ° F ______________ __ 277 midity is in excess of about 55 percent, e.g., 75 percent, Recovery, percent __________________ __ 98.3 99 percent. The optimum proportion of the antistalling Residue, percent ____________________ __ 1.4 addition ‘agents disclosed herein in any given case will be 10 sufficient to effect substantial reduction in the stalling (b) The addition agent of Example 1(a) was incorpo tendencies of the -fuel at the particular atmospheric con rated in the base gasoline of Example 1(a) in propor ditions of temperature and humidity which are likely to tion of 15 pounds per thousand barrels of gasoline. be encountered in service. Practically speaking, the problem of engine stalling due EXAMPLE II to carburetor icing caused by rapid evaporation of gaso (a) The addition agent of Example 1(a) was incor line occurs only in connection with gasolines having a porated in a base gasoline in the proportion of 250 50 percent ASTM distillation point less than 235° F. pounds per thousand barrels of gasoline. In this compo While occasional engine stalling may occur as a result of carburetor icing at severe atmospheric conditions of 20 sition the base gasoline had the following inspections. temperature and humidity with gasolines having somewhat Inspections: higher 50 percent ASTM distillation points, experience Gravity, has indicated that the problem does not assume major Existent gum, mg./100 ml _______________ __ Oxidation stability, minutes ______________ __ importance except with gasolines of the character in dicated. As indicated, the problem of engine stalling due 25 to carburetor icing is especially severe in connection with gasolines having a 50 percent ASTM distillation point of less than about 220° F. The invention is particularly useful in connection with such gasolines. The term “gas ° API _________________________ __ 62.6 557 Knock rating Motor Method, octane number _______ __ 84.4 Research Method, octane number _____ __ 95.4 TEL, ml./Gal __________________________ __ 3.19 Vapor pressure, Reid, lb ________________ __ oline” is used herein in its conventional sense to include 30 8.4 ASTM distillation, gasoline— hydrocarbon mixtures having a 90 percent ASTM distilla Over point, “P ____________________ __ 100 tion point of not more than about 392° F. and a 10 per End 10% 50% 90% 394 135 210 316 cent ASTM distillation point of not greater than 149° F. The antistalling addition agents whose use is included by this invention can ‘be incorporated in the base gasoline fuel compositions in any suitable manner. Thus, they point, ° F _____________________ __ evaporated at ° F ______________ __ evaporated at ° F ______________ __ evaporated at ‘’ F ______________ __ Recovery, percent ___________________ _.. 97.6 can be ‘added as such to gasoline or in the form of dis Residue, percent ____________________ __ 0.9 persions or solutions in solvents such as butanol, iso propanol, ethanol, methanol, benzene, toluene, heptane, kerosene, gasoline, mineral lubricating oil, or the like, 40 which solvents may or may not themselves contribute to the antistalling characteristics of the gasoline motor fuel composition. If desired, the herein disclosed antistalling addition agents can be incorporated in gasoline fuel com positions in admixture with other materials designed to improve one or more properties of the gasoline, such as EXAMPLE III (a) A polyoxyethylene derivative of the stabilized ros in amine of Example 1(a) containing about 5 oxyethyl ene groups per molecule was blended with the base gaso line of Example Na) in the proportion of 25 pounds per thousand barrels of gasoline. The addition agent of ' this example contained approximately 15 percent free ros in amine which had no signi?cant effect on the stalling antioxidants, antigurnming agents, e.g., 2,6~ditertiarybutyl, characteristics of the gasoline. 4-methylphenol, antiknock agents, e.g., tetraethyl lead, (b) The addition agent of Example III(a) was incor lead scavenging agents, e.g., ethylene dibromide, ethylene porated in the base gasoline of Example 11 in the propor‘ dichloride, corrosion inhibitors, e.g., oil-soluble amine 50 tion of 250 pounds per thousand barrels of gasoline. phosphates, dyes, and the like. EXAMPLE IV The gasoline fuel compositions of this invention can be further illustrated by reference to the following speci?c (a) The salt of the stabilized rosin amine of Exam examples: ple 1(a) and oil-soluble petroleum sulfonic acids having EXAMPLE I 55 an average molecular weight of 392 was incorporated in a base gasoline containing 88 percent L-4 test fuel and (a) To a base gasoline, there was added a polyoxy 12 percent light thermally cracked gasoline distillate in ethylene derivative of a stabilized rosin amine (Rosin the proportion of 25 pounds per thousand barrels of Amine D) containing eleven oxyethylene groups per mol gasoline. The stabilized rosin amine sulfonate of this ecule, in the proportion of 25 pounds per thousand barrels of gasoline. The stabilized rosin amine referred to in 00 example had the following analysis: this example was a dehydroabietylamine having the formula: Rosin amine sulfonate _____________________ __ 52.0 Mineral oil 47.5 ___- _____ ___ Inorganic salts ____________________________ __ Trace Water 65 ___- Ash ____ __ Molecular _ _ 0.5 ___ 0 weight _________________________ __ 709 The base gasoline of this example had the following in \ spections. Inspections: Cr Gravity, ° API _________________________ __ 65.2 Existent gum, mg./100 ml ______________ __ 2.4 Oxidation stability, minutes ______________ __ 220 The base gasoline of this example had the following inspections. ~ TEL, 75 mL/gal __________________________ __ 2.52 Vapor pressure, Reid, lbs ________________ __ 7.7 3,025,147 5 Inspections-Continued ASTM distillation, gasoline Table B Over point, °F __________________ _v___ 1.01 End point, ° F____,_____ Engine test; Fuel composition avg. number stalls per 20 10% evaporated at '’ F___ ' cycles 50% evaporated at °F-,.____, _________ 90% evaporated at °F _____________ ._ 283 Recovery, Residue, percent _______ _.__ ___________ __ Inspections: °API _________________________ -_ 63.3 Existent gum, mg./ 100 ml _______________ __ Oxidation stability, minutes ______________ __ Example I(b). _ __.. _.-_ Example III(e). _-_ _.._ 10 Base fuel Example IV(a) _ . _ __..-- 3. 7 4. 7 6. 7 11.8 .... _. 5. 5 From the results set forth in Tables A and B, it will be seen that addition agents of the class described herein 15 effect a marked reduction in the carburetor icing and/or engine stalling tendencies of gasoline compositions in which they have been incorporated. While the addition agents employed in the above-indicated speci?c embodi 1.6 560 Knock rating, octane number_. ments are especially effective for the purposes of this invention, it is to be understood that the invention is Motor Method _____________________ __ 84.4 Research Method ___________________ __ 95.6 not limited to the use of these materials. Other addition agents of the class described herein can be substituted TEL, rnl./gal __________________________ __ 3.03 Vapor pressure, Reid, lbs ________________ __ 10. ,2 Example 1(a) ____________________________________ _.._ 1.0 (b) The addition agent of Example IV(a) was incor porated in a base gasoline in the proportion of 250 pounds per thousand barrels of gasoline. The base fuel of this example had the following inspections. Gravity, Base fuel percent __________________ __ 97.9 7.7 for those indicated in the preceding examples in the same or equivalent proportions with good results. For ex ample, there can be substituted in the above-indicated End point, ° F _____________________ __ 392 gasoline motor fuel compositions polyoxyethylene and 10% evaporated at 0F _____________ __ 139 polyoxypropylene derivatives of stabilized rosin amine 50% evaporated at “F _____________ __ 211 that contain, respectively, 20 and 7 oxyalkylene groups 90% evaporated at ° F ______________ _.. 3116 per molecule. Recovery, percent __________________ __ 97.7 30 The oil-soluble petroleum sulfonic acids whose sta~ Residue, percent ____________________ __ 1.1 bilized rosin amine salts are employed in the gasoline motor fuel compositions of this invention are preferably (c) The addition of agent of Example IV(b) was in the sulfonic acids known as the mahogany acids. These corporated in the base gasoline of Example II in the acids, together with the water-soluble green acids, are proportion of 250 pounds per thousand barrels of gaso produced during the sulfuric acid re?ning of petroleum line. lubricating oil distillates. Methods of recovering these The utility of the gasoline motor fuel compositions of acids, as well as methods of making amine salts thereof, this invention has been demonstrated by two different are well known and form no part of the present inven test procedures. In the one test, referred to hereinafter tion. as the Mock Fuel System Test, test fuel at about 50° F. 40 The term “stabilized rosin amine” as used herein is and air at about 60° F. and 75 percent relative humidity employed in its normal sense to mean a rosin amine are supplied at controlled rates to a glass vaporizer cham having the ring structure of a stabilized rosin acid, such ASTM distillation gasoline- Over point, "P ____________________ __ 103 25 ber maintained at an absolute pressure of 12 inches of Hg and having an initial temperature of 45° F. as dehydroabietic acid, dihydroabietic acid, tetrahydro The abietic acid, or a mixture of such rosin amines, unless time for icing to occur and/ or the amount of ice formed 45 speci?cally indicated to the contrary. on a movable brass throttle plate in the glass vaporizer To the gasoline fuel compositions of the present in chamber are observed and recorded. According to the other test procedure employed, here inafter referred to as the Engine Test, a 216 cubic inch vention there can be added one or more additional agents designed to improve one or more characteristics of the Chevrolet engine employing a standard, Carter downdraft gasoline fuel. For example, antioxidants, antiknock agents, ignition control additives, other de-icing agents, carburetor is operated at no load on a test stand under antirust agents, dyes, lead scavenging agents and the like cycling conditions in a cold room maintained at 40° F. can be added to the gasoline compositions of this inven for a warm-up period of 20 cycles. Each cycle com tion, and the invention speci?cally includes gasoline prises 40 seconds at 2000 r.p.m. followed by an idle for compositions containing such additives. 20 seconds at 450 rpm. Air is supplied to the carburet 55 Numerous additional embodiments of the invention will or at 40° F. and 80 to 90 percent relative humidity. readily suggest themselves to those skilled in the art. The number of engine stalls is observed and reported as Accordingly, only such limitations should be imposed on stalls per 20 cycles. The results obtained in the testing the invention as are indicated in the claims appended of the motor fuel compositions of the above-indicated ex hereto. 60 amples are presented in the following tables: We claim: 1. A gasoline motor fuel composition comprising a major amount of a hydrocarbon mixture boiling in the gasoline range and that normally tends to promote stalling of internal combustion engines, and a small amount, suffi 65 cient to reduce the engine stalling characteristics of the Table A Mock fuel system test composition of a member selected from the group con Fuel composition Extent of ice forma- Time to tion on throttle plate icing, min utcs Base fuel ____________________________ __ Example II ____ _. Example III(b)._ Example IV(c)_ Base in _ _ _ . _ . . _ . _ _ Example IV(b).. Very heavy ..... .. L‘ ht sisting of addition salts of stabilized rosin amine and an oil-soluble hydrocarbon sulfonic acid, and polyoxy alkylene derivatives of stabilized rosin amine containing 70 about 4 to 20 oxyyalkylene groups per molecule, where said oxyalkylene groups contain two to three carbon 7 atoms each. 15.2 1. 5 18.3 _ _ _ . _ _ _ _ . . __ __________ _. 2. The fuel composition of claim 1 Where the hydro carbon mixture has a 50 percent ASTM distillation point 75 not greater than 220° F. 3,025,147 7 3. The fuel composition of claim 1 wherein said small amount is 0.001 to 0.1 percent by weight of the com position. 4. The fuel composition of claim 1 where said small acount is about 15 to 50 pounds of said member per thousand barrels of said hydrocarbon mixture. 5. The fuel composition of claim 1 where said member is a salt of oil-soluble petroleum sulfonic acids and sta bilized rosin amine. 6. The fuel composition of claim 1 ‘where said member 10 is a polyoxyethylene derivative of stabilized rosin amine containing about 11 oxyethylene groups per molecule. 7. The fuel composition of claim 1 where said member is a polyoxyethylene derivative of stabilized rosin amine containing about 5 oxyethylene groups per molecule. 15 8. The fuel composition of claim 1 where said member References Cited in the ?le of this patent UNITED STATES PATENTS 2,484,010 2,684,292 2,706,677 2,843,464 2,857,253 2,862,800 2,872,303 2,883,276 Bried _______________ __ Oct. 11, Caron et al. _________ __ July 20, Duncan et al. ________ __ Apr. 19, Gaston et al. __________ __ July 15, Hinkamp et al. ______ __ Oct. 21, Cantrell et al. ________ __ Dec. 2, Donlan ______________ __ Feb. 3, Larsen ______________ __ Apr. 21, 1949 1954 1955 1958 1958 1958 1959 1959 FOREIGN PATENTS 791,394 Great Britain ________ __ Mar. 5, 1958 OTHER REFERENCES Petroleum Re?ning with Chemicals, by Kalichevsky et is a polyoxyalkylene derivative of stabilized rosin amine al., 1956, Elsevier Pub. Co., page 480. containing about 4 to 20 oxyalkylene groups per mole “New Sonneborn Sulfonates” (Brochure), L. Sonne cule, and where said oxyalkylene groups contain 2 to 3 born Sons, Inc., WO 1876-8-55, received in Pat. Off. carbon atoms each. 20 April 11, 1956, 4 pp.